Silver halide emulsions containing magenta-colored cyan couplers



s 1969 MAKOTO Y'OSHIDA 'ETAL 3,459,552

SILVER HALIDE EMULSIONS commumc MAGENTA-COLORED CQYAN COUPLERS- Filed Jan. 28, 1966 "Hon OPTICAL DENSITY 400' 450 560 550 600 WAVE LENGTH \N MlLLlMlCRONS OPTICAL DENSITY INVENTORS MAKOTO YOSHIDA LOG EXPOSURE AKIO OKUMURA KEISUKE SHlBA ATTORNEYS United States Patent office 3,459,552 SILVER HALIDE EMULSIONS CONTAINING MAGENTA-COLORED CYAN COUPLERS Makoto Yoshida, Akio Okumura, and Keisuke Shiba, Ashjgara-Kamigun, Kanagawa, Japan, assiguors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa, Japan Filed Jan. 28, 1966, Ser. No. 523,686 Claims priority, application Japan, Feb. 3, 1965, 40/ 5,664 Int. Cl. G03c 1/40 US. Cl. 96-100 13 Claims ABSTRACT OF THE DISCLOSURE A color photograph silver halide emulsion containing a magenta-colored cyan coupler represented by the following formula:

CONIIR /J wherein R is a mononuclear aryl radical substituted with at least one alkoxycarbonyl group having at least 9 carbon atoms; and R is a lower alkyl group.

The present invention relates to color photography and particularly color photographic materials containing improved colored couplers.

Almost all of the cyan couplers used as color formers in color photography are l-naphthl-2-carb0xylic acid derivatives or aminophenol derivatives.

In United States Patents 2,449,966 and 2,455,169 there are described colored couplers, of which the 4-position of the naphthol nucleus is substituted by an arylazo group, having color masking action for correcting the color deficiencie of color photography.

In United States Patent 2,521,908 there are described colored coupler compounds having the formula:

in which X is hydrogen or alkyl, Y is a mononuclear aryl radical, or an aralkyl radical and R is a mononuclear aryl radical. All the compounds described in this patent are yellow to orange-red in color, rather than the desired magenta color. In United. States Patent 2,706,684 there are described 1-hydroxy-2-naphthanilide colored coupler compounds having the above formula in which X is hydrogen, Y is mononuclear aryl radical substituted in a position ortho to the amido group with either halogen, alkoxy or mononuclear aryloxy radicals and R is a mononuclear aryl radical.

Patented Aug. 5, 1969 i t bl C-ORA wherein x is an integer from O to 4; y is an integer from O to 1; and R is a member selected from the group consisting of alkyl radicals containing from 6 to 15 carbon atoms, phenyl radicals, alkphenyl radicals in which the alkyl group contains from 1 to 15 carbon atoms, alkphenoxyphenyl radicals in which the alkyl group contains from 1 to 15 carbon atoms, and alkphenoxyphenyl radicals in which the alkyl group contains from 1 to 15 carbon atoms; R is an alkyl group having from 1 to 4 carbon atoms; and R is an alkyl group having 1 to 12 carbon atoms.

In the case of using these couplers in the emulsions for multi-layer color photographic films, in order to prevent the coupler from diffusing out of the coupler-incorporated layer, a long-chain alkyl group or a dialkylphenoxy group is introduced into the coupler molecule as a group for giving diffusion resistance to the couple-r. However, if an aryl group is introduced into the 2-position of the naphthol nucleus of a cyan colored coupler, as a method for improving the color, solubility in water-insoluble, high boiling point solvents (hereinafter these solvents are called simply coupler solvents) is lowered. Further, in the coupler in which a long-chain alkyl group, giving diffusion resistance to the coupler, is bonded to the aryl group of the coupler molecule by an acid amide bond which can be easily prepared, the solubility thereof in coupler solvents is lowered and hence the preparation of the emulsified dispersion of the coupler becomes difficult and the couper is easily crystallized in a photographic emulsion. In order to'overcome these difficulties, various improvements have been proposed.

However, these proposed couplers are mainly ones wherein a dialkylphenoxyphenyl group or a dialkylphenoxyalkyl group is introduced into the 2-position of the naphthol nucleus. The structures andthe preparation of such couplers are complicated, whichmakes the couplers very expensive in material and in preparation.

In Japanese Patent No. 508,680 there are disclosed couplers having a branched alkyl group at the 2-position of the naphthol nucleus as couplers having good solubility in coupler solvents, and being easily prepared.

These couplers have a very long wave length absorption maximum of 505 to 510 m However, cyan colored couplers having the longer wave length absorption maximum and a large green absorption are more profitable in color correction.

It is therefore an object of the present invention to provide magenta-colored cyan couplers which have sufiicient solubility in coupler solvents, and which are prepared by using inexpensive materials and simple procedures.

A further object is to provide magenta-colored cyan couplers having bathochromic absorption maximum and a large green absorption. Other objects will appear from the following description and claims.

These and other objects are accomplished by using couplers in which one or more higher alkoxycarbonyl groups are introduced to the aryl group at the 2-position of the naphthol nucleus according to this invention.

That is, couplers of this invention are selected from the group consisting of compounds with the general formula:

CONHR ZOOR' I C O O C2115 COO(CH2)2CH3 (II) (gII COO(CH2)11CH3 c ONE-Q C O 0211 (Ill) C 0 0C ll; (IV) (|)l[ ({UUKUHZMlU;

I I OCHs I t Q I C O OCzIl'r, (Ni ?0O(CL[2)HC] [3 CONE-Q I Cl I COOC2H5 (VI) EH5 on coooHzomoilzholn CONE- OCH;

COOCzlT (Vl ()0 ()(UUzhUIh I COOCz 5 3,459,552 5 6 H COMCHMOHS bonded to the aryl radical at the 2-position of the naphthol nucleus through an acid amide group.

' Table 1 I Coupler: Solubility CH3 5 (a) 1 CONE- 00002115 (XI) V 250 The results shown in the above table are obtained as 1 follows; that is, an excess amount of each of the couh plers of this invention and comparative couplers (a) and N-@ (b) are dissolved into a coupler solvent consisting of I tricresyl phosphate, with stirring, by heating at tempera- 00002115 I (XII) tures above 60 C. After allowing to stand for 6 days 0 H at 35 C., the amount of the coupler present in the satu- 2 5 rated solution as the dissolved state is measured spectro- 011 h KCmMCHu photometrically, and the thus obtained solubility is shown I by mol natio.

The optical absorption curves of the couplers of this invention and the comparative couplers in tricresyl phosphate are shown in FIG. 1 of the accompanying drawings.

1 That is, each of the couplers is dissolved in tricresyl N 3 phosphate, the optical absorption curves are measured and they are plotted in the figures by setting the maxi- I mum optical density to 1.0.

cooo ng (XIII) In FIG. 1, Curve (A) is the spectroscopic absorption curve of Coupler (I) of this invention, Curve (B) that of above-mentioned comparative Coupler (a) and Curve (C) that of comparative Coupler (0) described in Japanese Patent No. 508,680.

I From the results it is clear that the couplers of this @JC oNH-Q-C 0NH(CH2)11CH3 invention have good solubility in coupler solvents, which In addition, the following disclosed couplers are also used for comparison:

is several times to several hundred times those of conventional couplers having similar structures in which a I long-chain alkyl group endowing diffusion resistance to N the coupler is bonded to the aryl group at the 2-position Q Q r of the naphthol nucleus through an acid amide bond, and that the very profitable eflects can be obtained by IJOOCZHE introducing a higher alkoxycarbonyl group to the aryl (a) group at the 2-position of the naphthol nucleus.

(32H5 Moreover, as to color, the couplers of this invention have maximum absorption at longer wave length than CONHCHZOmCHmCH that of the coupler described in Japanese Patent No. O 508,680, which is very profitable in color correction effect. Furthermore, the maximum absorption of the (30m coupler of this invention is at a little longer wave length than those of the coupler having an aryl group at the 2-position of the naphthol nucleus, but having a longchain alkyl group bonded to the aryl group by an acid Q amide bond and the couplers having no substituents at the aryl group. Accordingly, the introduction of a higher (30002115 (b) alkoxycarbonyl group to the aryl radical at the 2-position OH r of the naphthol nucleus is profitable in this point also.

1 C2115 Other advantages of the couplers of this invention will ooNil-ol-rgdmoflmom become clear from the following examples of the prepara- 7 tion of the couplers and the following examples of this J invention. I The couplers used in this invention can be prepared very easily using inexpensive raw materials by the following three reaction steps:

, (a) An ester-exchange reaction of a lower alcohol y 10002115 (c) ester of an aromatic carboxylic acid having an amino The solubilities of con lers ofthis invention are shown group, in the following table together with those of comparative A wndensatfofl feactlofl the l g alcohol ,couplgfs and (b hi h diff t from h ester of the aromatic carboxylic acld having the amino plers of this invention only in that a long-chain alkyl group andl-hydroxy-Z-naphthoic acid phenyl ester, and group, for giving ditfusion resistance to the coupler, is (c) A diazo coupling reaction with the mother coupler.

Typical examples of preparations of the couplers are as follows:

(1) 1-hydroxy-4- 2-ethyloxycarbonylphenylazo) -2- 4- dodecyloxycarbonyl -naphthanilide (Structure I (1-A) DODECYL- t-AMINOBENZOATE In a 1,000 ml. three-neck flask were placed 165 g. (1 mol) of ethyl-4-aminobenzoate, 279 g. (1.5 mol) of n-dodecyl alcohol, and 3 ml. of titanium butoxide, and they were heated to l50160 C. with stirring. Nitrogen gas was introduced to accelerate the distillation of ethanol produced by the ester-exchange reaction. After 3 hours ethanol in an amount of about 80% of a theoretical amount was distilled 01f.

The product was mixed with 1,000 ml. of methanol and cooled to form crystals, which were collected by filtration and rinsed with 200 ml. of methanol. The recrystallization from methanol gave 221 g. (yield 73%) of the product. The melting point of the product was 82-84" C.

(1-B) 1-HYDROXY-2-( i-DODECYLOXYCARBONYL)- NAPHTHANILIDE In a 300 ml. flask were placed 61 g. (0.2 mol) of the dodecyl-4-amino-benzoate prepared by above step (1-A) and 53 g. (0.2 mol) of l-hydroxynaphthoic acid phenyl ester. The mixture was heated for 1 hour to 150160 C. and the phenol formed was removed by distillation under reduced pressure.

The product was dissolved in 300 ml. of ethanol and the solution was cooled by ice to precipitate crystals, which were collected by filtration and rinsed with 100 ml. of methanol.

Thus, recrystallization from 250 ml. of ethanol gave 60 g. (yield 63%) of the product. The melting point of the product was 126-128" C.

(1C) 1 HYDROXY-4-(2-E'IHYLOXYCARBONYLPIIENYL- AZO) 2 (4 DODECYLOXYCARBONYL)-NAPHTHANI- LIDE In an aqueous solution consisting of 50 ml. of water and ml. of concentrated hydrochloric acid was dispersed 9 g. of Z-carbethoxy aniline and diazotized by adding, at temperatures less than 5 C., 4.5 g. of sodium nitrite in ml. of water.

The thus obtained diazonium salt solution was added at temperatures of below 8 C. in a solution of 24 g. of the l-hydroxy-2-(4 -dodecyloxycarbonyl) naphthanilide, obtained by above-mentioned (l-B), in 400 ml. of pyridine to conduct coupling and the thus precipitated crystals were collected by filtration, rinsed with 1,000 m1. of water containing 50 ml. of hydrochloric acid and further 2,000 ml. of water, recrystallized from 500 ml. of diethyl formamide, and then rinsed with 100 ml. of methanol. By the treatment, 30 g. (yield 91%) of the coupler was obtained. The melting point of the coupler was 165l66 C. and the analytical value of nitrogen was 6.26% (calculated 6.46%

(2) 1-hydroXy-4-(2-propyloxycarbonylphenylazo-Z-(4- dodecyloxycarbonyl)naphthanilide (Structure II) The above coupler was obtained by repeating the same procedure as in above-mentioned procedure (lC) using Z-carbopropyloxy aniline instead of 2-carbethoxy aniline. The yield was 83%, the melting point of the product was l57-158 C., and the analytical value of nitrogen was 6.25% (calculated 6.32%).

(3) 1 hydroxy 4 (2 ethyloxycarbonylphenylazo)-2- (2 chloro-S-dodecyloxycarbonyl)naphthanilide (struc ture VI) (34: 1 HYDROXYA-(2-ETHYLOXYCARBONYLPHENYL- BONYL) NAPHTHANILIDE The above compound was obtained by repeating the procedure as in above-mentioned procedure (1-B) using dodecyl-4-chlorobenzoate instead of dodecyl-4-aminobenzoate followed by recrystallization with petroleum ether. The yield was 70% and the melting point of the product was 4950 C.

3-13) 1 HYDROXY-l-(2-ETHYLOXYCARBONYLPHENYL- AZO) 2 (2 CHLORO-E-DODECYLCARBONYL)NAIII- THANILIDE The above coupler was obtained by repeating the procedure as in above-mentioned procedure (1-C) using the l-hydroxy-2-(2-chloro 5 dodecyloxycarbonyl)naphthanilide prepared by above step (3-A) instead of l-hydroxy-2-(4-dodecyloxycarbonyl)naphthanilide. The yield was 91%, the melting point was 147 C., and the analytical value of nitrogen was 6.03% (calculated 6.13

(4)-l hydroxy-4-(2 ethyloxycarbonylphenylazo)-2-(2- methyloxy-5-(2 ethylhexyloxycarbonyl) )naphthanilide (Structure VI) (4-A) (2-ETHYLHEXYL)-3-AMINO 4-METHYLOXY- BENZOATE The ester-change as in above-mentioned one l-A) was conducted using methyl-3-amino-4-methyloxybenzoate and 2-ethylhexyl alcohol instead of ethyl-4-aminobenzoate and n-dodecyl alcohol respectively. By removing excessive 2- ethylhexyl alcohol from the reaction mixture by distillation under reduced pressure, the oily product was obtained.

(4-B) 1-HYDROXY-2-(2-METIIYLOXY-5-(2-ETHYL- HEXYLOXYCARBONYL) )NAPHTHANILIDE By repeating the procedure as in above-mentioned step (l-B) using the (2-ethylhexyl)-3-amino-4-methyloxybenzoate prepared by procedure (4-A) instead of dodecyl-4- aminobenzoate, the above compound was obtained. The yield was 68% and the melting point was 84-85 C.

(:l-C) 1 HYDROXY- i-(2-E'lHYLOXYCARBONYLPHENYL- AZO)-2-(2-METHYLOXY 5 (2-ETHYLHEXYLOXYCAR- BONYL) )NAPHTHANILIDE By repeating the procedure as in step (1-C) using the 1-hydroxy-2( 2-methyloxy-5 2 ethylhexyloxycarbonyl) naphthanilide prepared in (4-B) instead of 1-hydroxy-2- (4-dodecyloxycarbonyl)naphthanilide, the above coupler was obtained. The yield was 96%, the melting point was 148-150 C. and the analytical value of nitrogen was 6.73% (calculated 6.72%).

(5) 1-hydroxy-4-(2-ethyloxycarbonylphenylazo)-2-(3,5- diotyloxycarbonyl)naphthanilide (Structure VIII) (ES-A) DIOXTYL-S-AMINOISOPHTHALATE The above compound was obtained by repeating the procedure as in above-mentioned procedure (l-A) using dimethyl-3-aminiosophthalate instead of ethyl-4-amin0- benzoate and using 3 mols of n-octyl alcohol per 1 mol of dimethyl-3-aminoisophthalate instead of n-dodecyl alcohol. The yield was 62% and the melting point was 82- 83 C.

(545) 1-HYDROXY-2-(3,5-DIOCTYLOXYCARBONYL) NAPHTHANILIDE The above compound was obtained by repeating the procedure as in (1B) using the dioctyl-3-aminoisophthalate prepared in (S-A) instead of dodecyl-4-aminobenzoate followed by recrystallization with petroleum ether. The yield was 71% and the melting point was 9496 C.

(5-C) 1 HYDROXY-4(2-ETHYLOXYCARBONYLPHENYL- AZO) 2 (3,5 DIOCTYLOXYCARBONYL)NAPHTHANI- LIDE By repeating the procedure as in (1-C) using the 1- hydroxy 2 (3,5-dioxtyloxycarbonyl)naphthanilide prepared in above step (S-B) instead of l-hydroxy-2-(4- dodecyloxycarbonyl)naphthanilide, the above coupler was obtained. The yield and the melting point of the product were 92% and l43l45 C. respectively and the analytical value of nitrogen was 5.28% (calculated 5.59%).

9 t The following examples areintended to illustrate our invention but not to limit it in any way. V

EXAMPLE 1 Into 10 parts of tricresyl phosphate was dissolved 1.25 parts of the coupler having structure (I) by heating to 80 C. and the solution was mixed with 100 parts of an aqueous 10% gelatin solution pre-heated to 60 C. The solution was further mixed with 2 parts of-an aqueous 10% solution of sodium alkylbenzene sulfonate and the system was stirred for 5 minutes by using a high speed rotary mixer at about 65 C. with an interruption of 1 minute, the stirring being repeated 5 times to give an emulsified dispersion of the coupler.

Into 100 parts of a silver iodo-bromide light-sensitive emulsion containing a panchromatic sensitizer there was added 13.5 parts of the above-prepared emulsion, at 35 C., with stirring and the mixed emulsion was coated on a film base and dried to give a red-sensitive color photographic light-sensitive material.

The film was exposed to red light using an optical wedge and developed as usual in a color developing solution having the following composition:

Color developing solution:

N,N-diethyl-p-aminoaniline sulfate g 20 Sodium sulfite g 2.0 Sodium carbonate (mono-hydrate) g 50.0 Hydroxylarnine hydrochloride g 1.5 Potassium bromide g 1.0 Water to make (pH 10.8:01) ml 1000 The developed photographic film was then bleached and fixed using a bleaching solution and a fixing solution having the following compositions respectively to remove the undeveloped silver halide and reduced silver:

Bleaching solution:

Potassium ferricyanide g 100 Potassium bromide g 20 Water to make (pH 6.9:03) ml 1000 Fixing solution:

Sodium thiosulfate g 200 Sodium sulfite g 20 Acetic acid (28%) ml 45 Boric acid Q. g 7.5 Potassium alum g 20 Water to make (pH 45:0.2) rml 1000 By the treatment, a positive red image having very exeellent transparency and a cyan-colored negative image were obtained. The maximum absorption of the positive red image was at the wave length of 518 mu.

EXAMPLE 2 Into parts of tricresyl' phosphate was dissolved 1.25 parts of each of the couplers shown in Table 2 by heating to 80 C. and the solution was mixed with 100 parts of an aqueous 10% gelatin solution pre-heated to 60 C. The solution was further mixed with 28 parts of an aqueous 10% sodium hydroxide solution of the cyan coupler shown by the following structural formula:

CONHC1QIT31 l S OsNa followed by stirring for minutes at about 65 C. using a high speed rotary mixer and the system was neutralized with citric acid to give an emulsified dispersion of coupler.

The above-prepared emulsified dispersion of coupler (10 parts) was mixed with 100 parts of a silver iodobromide lightsensitive emulsion containing a panchromatic'sensitizer and the mixture was applied on a film support as in Example 1'to give a color photograph lightsensitive material.

The film was exposed to red light using an optical wedge, developed, bleached and fixed as in Example 1 to give a positive red image having very excellent transparency and a cyan-colored negative image. The maximum absorption wave length thereof is shown in the following table.

Table 2 Maximum absorption wave length Coupler: (mi) of positive red image (0) 510 (III) 518 (IV) 516 (V) 517 (VI) 518 (VII) 51-8 (VIII) 520 (X) 518 (XII) 520 (XIII) 520 NoTn-Coupler (c) in the above table is the aforementioned comparative known coupler.

EXAMPLE 3 Into 10 parts of dibutyl phthalate were dissolved 1.25 parts of the coupler of this invention having structure (I) and 2.5 parts of the cyan coupler having the following structure:

by heating to C. and the solution was treated as in Example 1 to give an emulsified dispersion of coupler. The dispersion was mixed with a silver halide light-sensitive emulsion and coated on a film base as in Example 1 to give a red-sensitive color photographic light-sensitive material. The photographic film was then exposed, colordeveloped, bleached and fixed to give a positive red image having very excellent transparency and a cyan-colored negative image.

By the positive red image the blue to green unnecessary absorptions of the cyan dye can be corrected. This is practically shown in FIG. 2, wherein R shows the characteristic curve in the case of using a red filter, G the characteristic curve in the case of using a green filter, B the characteristic curve in the case of using a blue filter.

What we claim is:

1. A color photographic silver halide emulsion containing a color coupler having the following general formula:

GONHR 1 1 1 2 wherein R is a mononuclear aryl radical substituted with 6. The color photographic silver halide emulsion as at least one alkoxycarbonyl group having at least 9 carclaimed in claim 1 wherein said color coupler is bon atoms; and R is a lower alkyl group. I

2. The color photographic silver halide emulsion as on ooowumcn; claimed in claim 1 wherein said color coupler is l JCONII- on l 10 r -ooNii--( CUUlCliz)nk ll:i N OJ (300mm 1% 7. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is oooomcmomhoin claimed in claim 1 wherein said color coupler is l 1 N u on ooowimucin CONH i COOCEHS 8. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is on 3. The color photographic silver halide emulsion as gfi I i N on ooowiimcin IOOCzH5 CONE- COO CH CH 40 2)7 a l 4. The color photographic silver halide emulsion as m claimed in claim 1 wherein said color coupler is N- OH cfoowumcul 9. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is CONE- on poowlimcir, i C -Q H N 000cm t O 5. The color photographic silver halide emulsion as C OwHmCHa claimed in claim 1 wherein said color coupler is 10. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is OH (|]OO(CH2)iiCH3 OH COO(CH2)9CH T -Q 3 I 1 l OCH \l/ 3 N I I COOCzH COOCzHs 13 14 11. The color photographic silver halide emulsion as 13. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is claimed in claim 1 wherein said color coupler is OH COO(CH2)11CH3 c2115 CONH- 5 OH coocmomcmmrr, \J I CQNHQ @J ooocrHr 12. The color photographic silver halide emulsion as claimed in claim 1 wherein said color coupler is 00002115 OH COO(CH2)1CH3 A References Cited UNITED STATES PATENTS 2,521,908 9/1950 Glass et a1. 96-400 L 2,706,684 4/1955 Graham et a1. 96-100 2,808,329 10/1957 Whitmore 9610() 3,034,892 5/1962 Gledhill et al. 96100 1 COO 2 s J. TRAVIS BROWN, Primary Examiner 

